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Volume 21 | Number 10 | 14 March 2011 | Pages 32533496

Graphene and carbon nanomaterials


ISSN 0959-9428

FEATURE ARTICLE H. Liu et al. Chemical doping of graphene

FEATURE ARTICLE

www.rsc.org/materials | Journal of Materials Chemistry

Chemical doping of graphene


Hongtao Liu,ab Yunqi Liu*a and Daoben Zhua
Received 2nd September 2010, Accepted 14th October 2010 DOI: 10.1039/c0jm02922j Recently, a lot of effort has been focused on improving the performance and exploring the electric properties of graphene. This article presents a summary of chemical doping of graphene aimed at tuning the electronic properties of graphene. p-Type and n-type doping of graphene achieved through surface transfer doping or substitutional doping and their applications based on doping are reviewed. Chemical doping for band gap tuning in graphene is also presented. It will be benecial to designing high performance electronic devices based on chemically doped graphene.

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1. Introduction
Graphene, a single layer of sp2-bonded carbon atoms, has many unique physical properties such as ambipolar electric eld effect,1 high mobility of charge carriers (200,000 cm2 V1 s1),2,3 anomalous quantum Hall effect (QHE)46 and massless relativistic carriers,5 all of which make graphene appropriate for many potential applications including graphene nanoribbon (GNR) transistors, single molecule gas detectors, supercapacitors and transparent conducting electrodes. Moreover, eld-effect transistors (FETs) based on graphene are now considered a candidate for post-silicon electronics.7 Modern logic circuits are based on silicon complementary metal oxide semiconductor (CMOS) technology. Both p-type and n-type conductions are desired to construct complex logic circuits. Chemical doping is an effective method to tailor the electrical properties of graphene. Although pristine graphene exhibits ambipolar eld effect, it is not air stable and sensitive to unintentional doping by species absorbed from the surroundings8 or residual polymers used during device fabrication. Most graphene based transistors with ambipolar

eld effect are measured in a vacuum, nitrogen or argon and/or by annealing treatment. There is no water and other species easily affecting the electrical properties of graphene1,912 under those conditions. So, it is important to modulate the electronic properties of graphene by controlled doping with holes or electrons and reduce unnecessary contamination. This paper is concerned with a review of experimental studies of the chemical doping of graphene. p-Type and n-type doped graphene through surface transfer doping and substitutional doping will be discussed, and doping for band gap tuning in graphene is also presented. For a thorough discussion focused on synthesis, chemistry of graphene or graphene oxide and applications, see several excellent reviews.7,1320

2. Mechanisms and characterization of chemical doping


Graphene is made out of sp2 hybrid carbon atoms with the s, px and py atomic orbitals on each carbon atom forming three strong s bonds with other three surrounding atoms. Overlap of the remaining pz orbital on each carbon atom with neighboring carbon atoms produces a lled band of p orbitals, called the valence band and a empty band of p* orbitals known as the conduction band. The valence and conduction bands touch at the Brillouin zone corners thus making graphene a zero-bandgap semiconductor.24 Fig. 1A shows the energy spectrum of

a Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China. E-mail: liuyq@iccas.ac.cn b Graduate University of the Chinese Academy of Sciences, Beijing, 100049, P.R. China

Hongtao Liu was born in August 1983. He received his B.S. degree in Applied Chemistry from Qingdao University (2007). Then, he joined the Institute of Chemistry, Chinese Academy of Sciences (CAS) as a Ph.D. candidate. His research interests include synthesis of graphene derivatives and investigation of their physical properties.
Hongtao Liu Yunqi Liu

Yunqi Liu was born on April 1, 1949. He graduated from the Department of Chemistry, Nanjing University in 1975, and received a doctorate from Tokyo Institute of Technology, Japan, in 1991. He is currently a professor of the Institute of Chemistry, CAS. His research interests include molecular materials and devices.

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graphene and zoom-in of the energy bands at one of the Dirac point (at the K or K0 points in the Brillouin zone or the intersection of the valence band and the conduction band).21 Graphene can be doped by electric eld (Fig. 1B),22 by adsorption of metal atoms and by substrate (Fig. 1C).23 The mechanism of chemical doping in graphene would resemble that of carbon nanotubes, however the latter is still controversial.2529 From a large amount of literature, doping of graphene may be briey classied as electrical doping,1,30,31 achieved by changing gate voltage, and chemical doping,22,32 obtained by using chemical species. It can be seen in Fig. 1B that pristine graphene exhibits strong ambipolar eld effect indicating the doping of electrostatic potential. Fig. 1C shows the shift of the Dirac point relative to the Fermi level induced by chemical doping. In this review, we focus on the chemical doping of graphene. It is discussed in the following categories: surface transfer doping and substitutional doping.14,20 For surface transfer doping,33,34 doping is achieved by electron exchange between a semiconductor and dopants which adsorb on the surface of a semiconductor. Consequently, surface transfer doping is also called adsorbate-induced doping. In general, surface transfer doping does not disrupt the structure of graphene and most cases of chemical doping can be reversible. However, substitutional doping refers to the substitution of carbon atoms in the honeycomb lattice of graphene by atoms with different number of valence electrons such as nitrogen and boron. The incorporation of foreign atoms would disrupt sp2 hybridization of carbon atoms. Furthermore, substrate, residual chemical species and ambient air can induce involuntary doping.5,3537 Surface transfer doping occurs through charge transfer from the adsorbed dopant (or graphene) to graphene (or dopant).23,29,33 Charge transfer is determined by the relative position of density of states (DOS) of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the dopant and the Fermi level of graphene. If the HOMO of a dopant is above the Fermi level of graphene, charge transfers from dopant to the graphene layer, and the dopant acts as a donor; if the LUMO is below the Fermi level of graphene, there is a charge transfer from graphene layer to dopant,21,38 and the dopant acts as an acceptor. Graphene can be p-type or n-type doped via chemical doping.32,3840 p-Type doping drives the Dirac points of graphene above the Fermi level, and ntype doping drives the Dirac points below the Fermi level.

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Fig. 1 (A) Left: the band structure of graphene in the honeycomb lattice. Right: zoom-in of the energy bands close to one of the Dirac points. Reprinted with permission from ref. 21, copyright (2009) by the American Physical Society. (B) Ambipolar electric eld effect in single-layer graphene. The insets show the position of the Dirac point and the Fermi energy EF of graphene as a function of gate voltage. Reprinted with permission from ref. 22, copyright 2007, Nature Publishing Group. (C) A schematic diagram of the position of the Dirac point and the Fermi level as a function of doping. The upper panel is n-type doped, pristine and ptype doped free standing graphene (a to c). The lower panel is n-type doped, pristine and p-type doped epitaxial graphene grown on silicon carbide (SiC) (d to f). Reprinted with permission from ref. 23, Copyright 2008, American Chemical Society.

Daoben Zhu is a professor and Director of the Organic Solids Laboratory in the Institute of Chemistry, CAS. He nished his graduate courses at the East China University of Science and Technology in 1968. He was selected as an academician of CAS in 1997. His research interests include molecular materials and devices.

Daoben Zhu

Generally speaking, molecules with electron withdrawing groups adsorbed on the surface of graphene will lead to p-type doping of graphene, and molecules with donating groups will lead to n-type doping. In contrast, the mechanism of substitutional doping still remains uncertain. p-Type doping is generally achieved by adding atoms with fewer valence electrons than carbon like boron, while n-type doping is generally achieved by adding atoms with more valence electrons than carbon like nitrogen. Chemical doping of graphene has so far been extensively characterized by these three main kinds of methods: photoemission spectroscopy (PES), especially X-ray photoelectron spectroscopy (XPS) and angle-resolved photoemission spectroscopy (ARPES), Raman spectroscopy and transport measurement. From spectrum of XPS, we can nd whether the dopant exists by the characteristic peak of element contained in the dopant. The doping level can be determined by areas of the peak. The chemical states and electric states of the element could be obtained by analyzing the high resolution spectra of the element. ARPES is widely used to probe the electronic structure of graphene.4143 The band structure of graphene at Fermi level near the K point in the Brillouin zone can be obtained from the energy dispersions as a function of momentum along highsymmetry directions measured by ARPES. Fermi level locates at zero bonding energy, while the Dirac point is near, below or
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above the Fermi level depending on whether the graphene is pristine or doped. Raman spectroscopy is a powerful tool for monitoring the number of layers, disorder and doping of graphene.44,45 Due to relatively easy identication of single- and few-layer graphene akes by optical microscopy on silicon substrates with typically 300 nm SiO2, most of Raman studies are performed on graphene deposited on standard Si/SiO2 (300 nm).22 For electrically doped graphene, it is well known that the G band stiffens and upshifts for both electron and hole doping.31,46 The full-width at halfmaximum (FWHM) of G band also decreases for both kind of doping. Raman G peak is also sensitive to chemical doping and there is a useful empirical rule used to determine the doping type for surface transfer doping of graphene. n-Type doped graphene, or adsorption of molecules with electron-donating groups, the G band downshifts and stiffens; p-type doped graphene, or adsorption of molecules with electron-withdrawing groups, it upshifts and softens (Fig. 2).14,4749 The ratio of the density of the 2D band and the G band (I2D/IG), is sensitive to both kinds of doping. The asymmetry of the G band or the G band splitting induced by adsorption of aromatic molecules has also been reported.50 For substitutional doping, it would be different. It has been reported that both nitrogen and boron substitutionally doped graphene have an upshift of the G band.51 Electrical conductivity or resistance of n-type and/or p-type doped graphene can be measured by eld effect devices. The relationship between the conductivity or resistivity and gate voltage of pristine undoped graphene is a characteristic V-shaped curve. Typically, the minimum conductivity (or maximum resistivity) point or the Dirac point of pristine undoped graphene is at the zero gate voltage, and the point shifts toward positive (negative) gate voltage as a consequence of p-type (n-type) doping of graphene. If the band gap opens, graphene-based transistors will have higher on/off current ratio.

3. Surface transfer doping


3.1 p-Type doping In 2004, Novoselov et al.1showed for the rst time that freestanding 2D atomic crystal graphene stably exits with strong ambipolar eld effect and they also found that it can be doped by electric eld or chemical species. The electric eld doping transforms the zero-band-gap semiconductor into completely electron or completely hole conductor (Fig. 1B). Water vapor and ammonia lead to p-type and n-type doping of graphene respectively. During water vapor exposure, the resistance decreases and recovers to its original state when water vapor is removed.1,29 The resistance of graphene decreases rapidly when the device is exposed to NO2 gas (Fig. 3b).29 NO2 dopes holes into graphene and the minimum conductivity point shifts toward positive gate voltage without limiting carrier mobility (Fig. 3c) and changing the shape of the transfer characteristic of graphene-based FET. The doped graphene can be recovered by annealing at 150  C. Those observations have been interpreted by calculations.32 The adsorbed molecules neutralize the charged impurities in the substrate, thereby enhancing the carrier mobility. The mechanism of NO2 doping has been theoretically and experimentally investigated by Wehling et al.40 The Fermi level of NO2, exactly at the partially occupied molecular orbital (POMO), is about 0.4 eV below the Dirac point of graphene independent of adsorption conguration. Therefore, the NO2 molecule is a strong electron acceptor and accepts one electron from graphene. Adsorbed Br2 and I2 on one

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Fig. 2 Raman shift of the G band of graphene on interaction with (a) 1 M solutions of monosubstituted benzenes and (b) with varying concentrations of aniline and nitrobenzene. Reprinted with permission from ref. 47, copyright 2008, the Royal Society of Chemistry.

Fig. 3 (a) Concentration, On, of chemically induced charge carriers in single-layer graphene exposed to different concentrations, C, of NO2. Lower inset: characterization of the graphene device by using the electric eld effect. (b) Changes in resistivity, r, at zero B caused by graphenes exposure to various gases diluted in concentration to 1 ppm. The positive (negative) sign of changes is chosen here to indicate electron (hole) doping. (c) Constant mobility of charge carriers in graphene with increasing chemical doping. The parallel shift implies a negligible scattering effect of the charged impurities induced by chemical doping. Reprinted with permission from ref. 29, copyright 2007, Nature Publishing Group. (d) Schematic drawings of the charge transfer at the F4-TCNQ/graphene interface. Reprinted with permission from ref. 52, copyright 2007, American Chemical Society.

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layer of graphene inject high density of holes in graphene through charge transfer leading to p-type doping of graphene.53 Surface adsorbed molecules with electron-withdrawing groups can induce p-type doping effect of graphene. Tetrauoro-tetracyanoquinodimethane (F4-TCNQ) is a strong electron acceptor and widely used to improve the device performance of organic light-emitting diodes (OLEDs) and carbon nanotubes.5459 Chen et al.52 demonstrated that epitaxial graphene (EG) can be p-type doped by adsorbing F4-TCNQ on its surface (Fig. 3d). Synchrotron-based high-resolution photoemission spectroscopy (PES) reveals that electrons transfer from EG to F4-TCNQ and it only occurs at the F4-TCNQ/EG interface. So, an electron accumulation layer in F4-TCNQ and a depletion layer in EG form at the interface and a p-type doping of EG is obtained. The hole density in EG can be controlled by the coverage of F4TCNQ. Later theory and experiment conrm that it is a simple and effective method to obtain p-type doped graphene.60,61 Other organic molecules with electron withdrawing groups can also lead to p-type doping of graphene, such as tetracyanoethylene (TCNE),62 tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA).49 However, there is no signicant charge transfer between EG and C60, which is an electron acceptor too, partially due to the lower electron afnity of C60, and hence the absence of p-type doping of EG.52 Under laser illumination, graphene reacts with benzoyl peroxide (BPO), leaving phenyl groups covalently bonded to basal plane of graphene.63 Electrons in graphene are excited by laser illumination and accepted by surface adsorbed BPO. The BPO radical anion decomposes leaving holes in graphene. Single layer and double layer graphene react with oxygen at low temperature leading to hole doped graphene.64 The doping effect might be caused by electron transferring from graphene to acceptors produced by the reaction, such as endoperoxides, hydroperoxides, and/or charge-transfer complexes, bound on the basal plane. Diazonium salts with electron acceptor groups dope graphene with holes.65 The electron conduction is suppressed by doping via producing potential barrier preventing electron injection from the graphene electrodes beneath the metal electrodes to the graphene in channel. A self-assembled monolayer (SAM) of uoroalkyltrichlorosilane (FTS) on graphene introduces ultra high level hole doping with hole density >1013 cm2.66 As the SAM is growing, the Dirac point of pristine graphene moves towards more positive gate voltage and the mobility (m) decreases. The SAM of FTS extracts electrons from graphene and the SAM serves as negative charged scatters at the interface of SAM and graphene. For longrange charged scatters, the mobility inversely depends on the density of charged impurities (nimp), 1/m f nimp.67 This is why the mobility decreases with SAM growth. Besides organic molecules, metal atoms with high electron afnity like bismuth, antimony and gold, adsorbed on the surface of graphene also lead to a similar shift of the Dirac point of EG.23,68 EG on silicon carbide (SiC) is n-doped by the substrate, as a result of this, the Dirac point of graphene shifts below the Fermi level (panel e in Fig. 1C). Surface adsorbed bismuth and antimony atoms extract electrons from EG, and the Dirac point shifts toward the Fermi level but not coincide with it, but in contrast, gold, with higher electron afnity, shifts the Dirac point into the unoccupied states inducing p-type doping of EG (panel f in Fig. 1C).
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Density functional theory (DFT) shows that charge transfer is driven by work function difference as well as the chemical interactions between metal substrate and graphene.69 It is expected that graphene will be doped with holes if the metal work function (WM) is higher than the graphene work function (WG) and doped with electrons if WG > WM. The crossover points from n-type to p-type doping is then at WG WM. The chemical interactions are strongly dependent on the distance between graphene and metal surfaces. For metals with weak interactions such as Al, Cu, Ag, Au and Pt, the Fermi level of graphene shifts without perturbing the graphene band structure when graphene adsorbs on the metal surface due to the work function differences and there is a crossover from n-type to p-type doping. At larger  the chemical interaction is very weak distance, i.e. about 5.0 A, and the crossover would then be at WM WG. While at equi the chemical interaction is librium distance, i.e. about 3.3 A, strong and the crossover point locates at about 5.4 eV. In other words, metals with work function 0.9 eV higher than graphene work function can just induce holes in graphene and lower WM induces electrons in graphene. 3.2. n-Type doping

Four-probe resistance measurement of graphene nds that the resistance of graphene changes when it is exposed to various gases such as water, ethanol and ammonia (Fig. 3b).1 Among those, ethanol and ammonia, both donors, dope graphene with electrons, that is, n-type doping. Conduction of this electron doped graphene decreases and the original state recovers when the dopants are removed. Ammonia is more difcult to remove than ethanol because of the strong interaction with graphene. Later experiments show that chemical doping of graphene by donors or acceptors doesnt deteriorate graphenes mobility but shifts the position of the Dirac points of graphene without any signicant changes in their shape of s(Vg) curves (Fig. 3c).29 However, the curves become broader around the minimum conductivity points. The doping effect may be due to charge transfer from adsorbed ammonia to graphene.70 The similar results were also found in potassium doped graphene.67,71 Additionally, as doping concentrations increase, the mobility of potassium doped graphene decreases and the asymmetry for electron versus holes increases (Fig. 4). These observations are most likely due to the high quality of samples, wellcontrolled environmental conditions with little unintentional charged impurities and high concentration doping.67 The doped potassium atoms are charged-impurity scatterers which limit carrier mobility. However, potassium is highly reactive, so this doping method is difcult to implement in device technology. Carbon nanotubes can be efciently doped by poly(ethylene imine) (PEI), an electron-donating polymer.72 Similarly, graphene can also be doped with PEI, which results in n-type behavior.65 The conduction asymmetry for holes and electrons is observed. Hole conduction is suppressed and electron conduction is preserved in graphene when it is doped by PEI as the result of imbalanced carriers injection from the graphene electrodes beneath the metal electrodes like the diazonium salts. Aromatic molecules with donating groups also lead to electron-doped graphene.49 The electron-doped graphene can be simply distinguished by Raman spectroscopy based on
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borane (NH3BH3) as precursors and a copper substrate as a catalyst.78 Pure h-BN and pure graphene domains randomly distributes in h-BNC and their compositions can be tuned by changing the ratio of the gas concentration, therefore, h-BNC with different band gaps are obtained. Because of its unique properties, it will have many potential applications in electronics. 4.2.
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n-Type doping

Fig. 4 The conductivity (s) versus gate voltage (Vg) curves for the pristine sample and three different concentrations of potassium doped graphene taken at 20 K in ultrahigh vacuum (UHV). Reprinted with permission from ref. 67, copyright 2008, Nature Publishing Group.

downshifting of the 2D and G bands without using expensive ARPES. It has been reported that adsorption of free radicals results in n-type doping of graphene.73 Graphene could also be n-doped by the substrate of SiO236,74 or silicon carbide (SiC)21,41 on which epitaxial graphene were grown. And the doping effect may be dependent on the interaction with the substrate.75 So that it is important to choose the proper substrate for graphene devices.76

4. Substitutional doping
4.1. p-Type doping It is worth recalling that one route for modifying the electronic properties of materials is the addition of electron donors or acceptors, which is a well known procedure in semiconductor technology. Compared to carbon, nitrogen has one additional electron and boron lacks one. When nitrogen atoms are incorporated into the basal plane of graphene, they denote electrons into graphene leading to n-type doping of graphene, which will be discussed later. As expected, graphene doped with boron would exhibit p-type behavior39 and boron doped GNRs would be a semiconductor.77 Boron doped graphene has been synthesized by Panchokarla et al.51 using arc discharge of graphite electrodes in the presence of H2, He, and diborane (B2H6). XPS demonstrates that B is bonded to the sp2 carbon network and the doping level is about 1.23.1%, slightly different to 1.02.4%, conrmed by electron energy loss spectroscopy (EELS). The intensity ratio of the Raman D band and G band (ID/IG) is higher than undoped graphene and the G band shifts to higher frequency as a result of B doping. The B-doped graphene exhibits higher conductivity and the Fermi level shifts 0.65 eV below the Dirac point by calculations indication the p-type doping of graphene. Recently, a large-area atomic thick lm of h-BNC consisting of hybridized hexagonal-BN (h-BN) and C (graphene) domains has been prepared by a CVD method using methane and ammonia
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Single-layer and few-layer nitrogen doped graphene sheets have been synthesized by a chemical vapor deposition (CVD) method with NH3 as the nitrogen source and their electrical properties were investigated.79 The nitrogen atoms are substitutionally incorporated into the basal plane of graphene in the forms of pyridinic, pyrolic and graphitic nitrogen bonding congurations revealed by X-ray photoelectron spectroscopy (XPS), which is illustrated in Fig. 5a. The pyridinic and pyrolic nitrogen may lie at the edge or the defect sites and the graphitic nitrogen refers to the nitrogen replacing carbon in graphene plane. The graphitic nitrogen is dominating and the doping level is about 8.9%, which can be controlled by the ratio of NH3 and CH4 in the feedstock. As a result of nitrogen doping, there are many ripples in the graphene sheets and high density of D bands in Raman spectra in most samples. Field-effect transistors based on pristine graphene and Ndoped have been fabricated. Compared with pristine graphene, N-doped graphene behaves like an n-type doped semiconductor with lower conductivity, lower mobility (about 200450 cm2 V1 s1) and larger on/off current ratio (Fig. 5b to 5d). The foreign nitrogen atoms may release electrons into graphene and modify the electronic structure of it, leading to n-type doping of graphene and opening the band gap. Nitrogen species can also be incorporated into the graphene plane through thermal annealing of graphene oxide (GO) in ammonia (Fig. 6a).10 It is demonstrated that ammonia reacts with oxygen functional groups in GO, giving rise to pyridinic and quaternary N-doped graphene during annealing (Fig. 6b), and GO is reduced simultaneously. The highest doping level is about

Fig. 5 (a) A schematic representation of the N-doped graphene. (b) Transfer characteristics of the pristine graphene and the N-doped graphene. (c) and (d) Ids/Vds characteristics at various Vg for the pristine graphene and the N-doped graphene FET device, respectively. The insets are the presumed band structures. Reprinted with permission from ref. 79, copyright 2009, American Chemical Society.

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Fig. 6 (a) A schematic of the structure of GO and its reaction with ammonia through thermal annealing. (b) High resolution N (1s) spectra of GO annealed in NH3 at 900  C. The peak is tted into low and high energy A and B components centered at 398.2 and 401.1 eV respectively. Letter A and letter B in (a) show the two predominant binding conditions of nitrogen in graphene annealed at high temperatures $900  C. (c) Current-gate voltage (IdsVgs) curves of a single GO device fabricated with an NH3-annealed (900  C) GO sheet. Reprinted with permission from ref. 10, copyright 2009, American Chemical Society.

5% with 500  C annealing. The doping level is stable with no signicant decrease when the N-doped reduced GO is annealed up to 900  C. Electrical measurements conrm that the conductivity of N-doped reduced GO is higher than GO annealed in H2. The minimum conductivity point (the Dirac point) of N-doped graphene is at negative gate voltage in vacuum and it shifts more negative after electrical annealing indicating the n-type doped effect (Fig. 6c). This method has also been used by others.80 The substitutional N-doping of graphene nanoribbons have been obtained by electrical joule heating (e-annealing) of GNRs in ammonia gas.11 During e-annealing, the GNR is self-heated up to about 300  C and the more reactive carbon atoms at the edge of the GNR can react with ammonia producing CN bonds. When the GNR is annealed in vacuum, the Dirac point of it is at positive gate voltage, typically at 5 to 20 V partially due to p-type doping of remaining oxygen groups at the edge. However, when it is e-annealed in ammonia and the excess and physisorbed ammonia is removed by a pump overnight, the Dirac point shifts about 20 voltages to negative gate voltage comparing with that eannealed in vacuum indicating the n-type doping of the covalently bonded nitrogen atoms. Because the main doping sites locate at the edge of the GNR, and there are no charged impurities in the plane of it, the carrier mobility is almost the same as it of the sample without doping. The N-doped graphene has also been synthesized by arcdischarge method51,81 and ammonia plasma82 treatment of graphene. Atomic layer graphene with boron nitride domains has been prepared by CVD method and the band gap of graphene opens up.78 Bottom-up synthesis of nitrogen doped GNRs has also been reported (Fig. 7a),8386 which will be a prospective way to synthesize n-type doped graphene with precise structure.
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Fig. 7 (a) Two tri(perylene bisimides) (triPBIs) isomers and their UV-vis absorption spectra. Reprinted with permission from ref. 83, copyright 2008, American Chemical Society. (b) UV-vis absorption spectra showing the change of GO dispersions as a function of reaction time. Reprinted with permission from ref. 87, copyright 2008, Nature Publishing Group.

5. Doping for band gap tuning in graphene


Graphene is a zero-band-gap semiconductor, so it is highly desired for inducing a gap in graphene for device applications. Many methods have been proposed to open the band gap in graphene such as substrate-induced band gap,75,8890 bilayer graphene9195 and connement and edge effects induced band gap such as graphene quantum dots96 and nanoribbons.97101 Some methods of opening the gaps can be found in another review.7 Chemical modication, like partially oxidation of graphite or controlled reduction of GO,102,103 hydrogenation,104 uorination,105 and chemical doping,42 is an alternate strategy to open a gap in graphene. There has been any amount of research on the synthesis, structures and properties of GO and reduced GO.16 It is well known that GO behaves like an insulator, while the electrical properties of reduced GO are similar to perfect graphene but with lower conductivity and mobility partly because of the residual oxygen functional groups and vacancy defects.35,106,107 Controlled oxidation of graphite or reduction of GO can induce band gap in graphene.108 Fig. 7b is a typical UV-vis adsorption
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spectra of GO and reduce GO.87 There is no clear leading edge in the adsorption spectra, which indicates the absence of a welldened band gap.16 However the defects in reduced GO can be used to tune the electrical properties of it,102 and the conductivity of GO can be controlled by reduction level.109 During reduction, the transitions from insulator to semiconductor then to semimetal have been observed.103 and reduced GO with semiconductor behavior has also been reported.110 Calculations have been demonstrated that adsorption of atomic hydrogen on graphene can open a substantial gap in graphene.111 Graphene reacts with hydrogen atoms forming CH bonds on the basal plane of graphene. Hydrogenation of graphene changes sp2-bonded carbon atoms into sp3-bonded ones and the conducting p-bands are eliminated thus opening the band-gap. The hydrogenated graphene can be restored by thermal annealing at 100200  C.112 It indicates that the electronic properties of graphene can be tailored by reversible hydrogenation of graphene. Graphane, hydrogenated graphene has been synthesized by Elias et al.104 Before hydrogenation, the device exhibits an ambipolar eld effect with the neutral point near zero gate voltage and QHE at low temperature (Fig. 8A and 8B) while the hydrogenated graphene behaves like an insulator (Fig. 8C and 8D). By thermal annealing in argon at 450  C, graphane converts back into graphene with its characteristic electrical properties (Fig. 8E and 8F), all of which are in line with the calculations. However, the recovery is not complete and the neutral point is not at the zero gate voltage but shifts to positive gate voltage indicating p-type doping of graphene (Fig. 8E). All the changes have been conrmed by Raman and TEM. It is easy to imagine that the band gap of hydrogenated graphene would be modulated by nely tuning the dosage of hydrogen atoms. The hydrogen atoms have also been detached by electron-stimulated desorption using a scanning tunneling microscope (STM) tip.113 The band gap does open by patterned hydrogenation of graphene.114 This is achieved by iridium catalyzed hydrogen chemisorption. The iridium lattice constant is different to graphene and a Moir e pattern (Fig. 9), which has a much larger periodicity, is generated when graphene grows on the top of Ir (111).115 The

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Fig. 9 a, the Moir e pattern formed by two sets of parallel lines. b, the Moir e pattern formed by graphenes honeycomb lattice on top of a triangular iridium (111) surface and two high-symmetry carbon iridium congurations: c, a carbon ring is centered above an iridium atom. d, a carbon atom sits on top of iridium. Hydrogenation preferentially takes place at carbon sites such as d, closest to peaks in the iridium landscape. Reprinted with permission from ref. 115, copyright 2010, Nature Publishing Group.

Fig. 8 Control of the electronic properties of graphene by hydrogenation. The electric eld effect for a device at zero B at various temperatures T (left column) and in B 14, T at 4 K (right). (A and B) The sample before its exposure to atomic hydrogen. (C and D) After atomic hydrogen treatment. (E and F) The same sample after annealing. Reprinted with permission from ref. 104, copyright 2009, the American Association for the Advancement of Science.

carbon atoms which are located nearest the top center surface of the iridium atom surface are preferentially hydrogenated giving rise to graphane-like islands and other spots remain clean (Fig. 9d). The hydrogen-free graphene regions become narrower as hydrogenation progresses and the band gap in hydrogenated graphene opens due to connement effect like graphene antidot lattices116,117 and graphene nanomesh.118120 The band gap is dependent of the hydrogen coverage or the dosage of atomic hydrogen. A band gap of at least 0.45 eV is observed by ARPES. The patterned hydrogenation of graphene has also been obtained by other methods.113 Like hydrogenation, uorination of graphene may also induce a gap. Theoretical calculation shows that only hydrogen and uorine can completely covalently cover the basal plane of graphene.105 Graphene uoride can be synthesized and exhibits insulator behaviors with large band gap while the reduced graphene uoride has low resistance.121 The gap may be tailored by different uorination level.122 Covalent attachment of aryl groups to the basal plane of graphene might induce band gap in graphene.123 The nitrophenyl groups modied epitaxial graphene is prepared by spontaneous reaction of the diazonium salt with the graphene layer. It is conrmed by Fourier transform infrared (FTIR) spectroscopy and XPS that the nitrophenyl groups are sp3-bonded to the surface of graphene. The coverage of nitrophenyl groups, estimated by cyclic voltammetry is about 1 1015 molecules cm2 on the graphene sheet. The resistance of the modied graphene increases and is dependent on the temperature suggesting the transform from a near-metallic conductor to a semiconductor. The band structure near the Dirac point of bilayer epitaxial graphene grown on the surface of SiC can be easily tuned by potassium doping.41 Fig. 10 is the energy-momentum curves and schematic illustrations of the evolution of band gap closing and reopening induced by potassium doping. The band structure is sensitive to the symmetry of the two layers. If the individual
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Fig. 10 Upper panel: closing and opening of the band gap in bilayer graphene induced by potassium adsorption on top of the bilayer stack. Lower panel: the Coulomb potential changes corresponding to the doping process.124 Reprinted with permission from ref. 41, copyright 2006, the American Association for the Advancement of Science.

layers in bilayer graphene are rendered inequivalent, then a gap opens. The as-prepared graphene is naturally n-type doped by the SiC substrate. The bottom layer is charged by electrons from the SiC substrate and then the electron concentration is different in the two layers. The Coulomb potential (Ei in Fig. 10) difference generates between the two layers. So the electronic structures of bilayer graphene possess a gap at the K point, which is observed in ARPES (Fig. 10a). The gap closes when adsorbed potassium donates electrons into the top layer and balances the charges in the bottom layer (Fig. 10c). It reopens when the charges of the top layer outweigh the charges of the bottom layer (Fig. 10d). Gaps can also be formed in graphene by molecular doping, such as NO2,42 Br2 and I2 adsorption.53 NO2 dopes graphene with holes as discussed above, and simultaneously induces a reversible metal to insulator transition in one layer and bilayer EG conformed by AREPS with a depletion of density of states at the Fermi level. For few-layer graphene, Br2 adsorbs and intercalates into graphene layers, in contrast I2 only adsorbs on the surface of graphene introducing different doping levels between surface and interior layers then creating symmetric potential (from two surfaces to the center) thus opening the band gap. Compared with other proposals for tuning band gaps, chemical doping is a simple and effective method to open a band gap in graphene. The gaps induced by chemical doping can be controlled by doping levels. Moreover, the original state of graphene can be restored by annealing.

would greatly simplify the use of graphene based sensors and even individual NO2 molecules can be detected.29 High performance sensors based on chemically derived graphene have been demonstrated.125129 Graphene-based biosensors for detecting bacteria,130 glucose,131 pH and proteins132,133 have also been fabricated. Detection of DNA targets based on GO has also been reported.134,135 And graphene may be an ideal material for DNA sequencing.136140 Experimental and theoretical studies have shown that graphene based pn junctions have many novel properties.141145 In most heterojunctions, the p-type and/or n-type region is formed by local top gate control. By selective chemical doping, pn junctions have been created and their properties have been investigated.146 One aim of chemical doping is to obtain controllable, air stable and high performance n-type, p-type or even ambipolar eld effect. As mentioned above, pristine graphene and reduced GO always show p-type behavior at ambient conditions because of unintentional doping caused by residual species or oxygen molecules in air, which is still not fully understood. However, when graphene is embedded in a insulating polymer matrix like polystyrene (PS), it is weakly sensitive to ambient doping and exhibits ambipolar eld effect.147 Although very high mobility is obtained in suspended graphene devices,2,3 graphene supported on chemically modied substrates, especially on hydrophobic substrates,148,149 or in aqueous solutions150,151 performs considerably well via screening the charged-impurity scatterings and reduction of doping. Graphene can be used as buffer layers between the electrodes and the organic semiconductors to enhance the performance of organic eld effect transistors (OFETs).152,153 The work function of graphene is similar to Ag or Cu electrode. Moreover, the molecular structure of graphene is similar to organic semiconductors like pentacene and the pp interactions between graphene and pentacene are very strong. All of those result in low carrier injection barrier and high performance of the device. Other applications have also been reported such as nitrogendoped graphene can be used as an efcient metal-free electrocatalyst for oxygen reduction in fuel cells80 and be doped with SOCl2 for high electrical conductivity.35 Because of the rapid progress on graphene, we believe other practical applications would emerge soon.

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7. Conclusions and perspectives


Herein, we have highlighted the important methods for modulating the electrical properties of graphene via chemical doping. p-Type and n-type doped graphene can be obtained through surface transfer doping and/or substitutional doping by different dopants. Some typical strategies to tune the band gap of graphene are illustrated, such as adsorption of chemical species i.e. atomic hydrogen, potassium, NO2, Br2 I2 and O2, controlled oxidation or controlled reduction and covalent modication. And the applications based on chemical doping are also mentioned. There are many challenges remaining at present. Most cases of surface transfer doping are obtained by adsorption of strong electron-donating or withdrawing chemical species. Because the adsorbed chemical species could desorb from graphene surface
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6. Doping, dedoping and their applications


Graphene is very sensitive to surface transfer doping and most doping processes are reversible. It is a two-dimensional material with large surface areas and ultra high conductivity which changes rapidly when gas molecules adsorb on the surface of it. All of them make graphene an excellent candidate for sensors with high sensitivity. It has been reported that its conductivity responses linearly to the concentrations of NO2, (Fig. 3a) which
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and the chemical species may react with reactive molecules such as oxygen or water from surroundings, doping of graphene would not have long-term stability. The substitutionally doped graphene would be more stable in that the foreign atoms are covalently bonded to the carbon network of graphene. The surface coverage of the chemical species or the number of foreign atoms incorporated into the basal plane of graphene is difcult to control and the doping of graphene would be difcult to reproduce. We need exact methods to homogenously and reproducibly dope graphene p-type/n-type for different applications and to control the doping level. And the doping mechanism is not fully understood, the relation between doping and mobility and band gap opening induced by chemical doping being among them. Doping caused by contaminations and the ambient air need to be investigated. However, tailoring the properties of graphene by chemical doping is considerably simple and high throughput doping of graphene is possible.

Acknowledgements
We acknowledge nancial support from the National Natural Science Foundation of China (60736004, 20721061), the National Major State Basic Research Development Program (2006CB806203, 2006CB932103, 2009CB623603), and the Chinese Academy of Sciences.

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This journal is The Royal Society of Chemistry 2011

J. Mater. Chem., 2011, 21, 33353345 | 3345